These are three distinct ways to maintain disequilibrium chemistry in an exoplanet atmosphere; each compares chemistry with a different transport or irradiation process.
For a representative hydrogen-rich hot Jupiter, increasing altitude lowers pressure, slows collision-driven chemistry, and increases exposure to stellar UV. Three principal regimes follow.
At high pressures, illustratively -- bar, collisions and sufficiently high temperature make thermochemical equilibrium a useful approximation. Molecular abundances minimize the free energy subject to elemental conservation. Condensation and atmospheric condensate rainout can remove selected elements from the gas.
At intermediate pressures, illustratively bar, vertical mixing and horizontal winds can outrun chemical relaxation time. The chemical quench level is defined by ; above it, some abundances retain values from a deeper or hotter region. Horizontal chemical quenching similarly occurs when chemical adjustment is slower than advection between the day and night hemispheres.
At low pressures, illustratively bar, atmospheric photochemistry becomes important: photodissociation and radical reactions change equilibrium abundances and can produce hydrocarbons and atmospheric hazes. At still lower pressures, roughly bar and above in altitude, photoionization and an escaping thermosphere can become important.
Figure 1.
Nominal deep-equilibrium, transport-quenching and photochemical regimes in a hydrogen-rich irradiated atmosphere
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These pressures label a representative sketch, not universal interfaces. UV optical depth, stellar spectrum, gravity, metallicity, reaction rates and eddy diffusivity determine the transitions; quenching is species-dependent.
Three solar-system effects illustrate chemical disequilibrium. First, vertical mixing carries carbon monoxide from hot deep regions into cooler observable layers of giant planets, where its local-equilibrium abundance would be small. Second, phosphine survives in the observable atmospheres of Jupiter and Saturn because deep supply competes with its destruction, making it a tracer of transport. Third, methane photolysis creates hydrocarbons such as ethane and acetylene, and can help form upper-atmospheric atmospheric hazes in giant planets and Titan.
Three exoplanet effects are complementary. First, carbon monoxide–methane quenching can keep carbon monoxide abundant and methane depleted in cool observable gas, including hot-Neptune/giant atmospheres that would locally favor methane. Second, atmospheric photochemistry dissociates methane/ammonia and produces radicals, hydrogen cyanide, hydrocarbons and possibly atmospheric hazes, changing spectral bands from their equilibrium strengths. Third, horizontal chemical quenching can preserve hot-dayside carbon chemistry on the cooler nightside/terminator and reduce the abundance contrast expected from separate local-equilibrium columns.
Transport, photon-driven reactions and finite chemical adjustment times change the observable composition. The effects are conditional on the species' chemical timescale relative to mixing, advection and irradiation; they do not imply that every molecule is out of equilibrium everywhere.
Convection mixes material vertically where the Schwarzschild criterion or Ledoux criterion allows it. Its chemical effect is controlled by competition between transport and reaction, rather than by a direct alteration of the equilibrium constant. Parametrize vertical transport by a vertical eddy diffusion coefficient ; the eddy mixing time over a scale height is
Let be the chemical relaxation time of the relevant interconversion. If reactions are faster, the gas follows local thermochemical equilibrium. If transport becomes faster, composition can be carried upward faster than it re-equilibrates. A chemical quench level is approximately where the two times match:
For example, hot deep gas may contain abundant carbon monoxide. Strong mixing can maintain it in cooler layers where equilibrium would favour methane; this is carbon monoxide–methane quenching. Similar reasoning applies to nitrogen–ammonia quenching. The cooler nightside commonly has slower reaction rates and can preserve such quenched composition more readily, whereas sufficiently rapid dayside chemistry can restore local equilibrium. Neither statement is universal without the actual reaction network and temperature.
The observable atmosphere of a strongly irradiated hot Jupiter may be radiative and stable even if the deeper interior is convective. Deep convection influences the photosphere only if some mixing crosses the intervening radiative region, for example through overshoot or other dynamical transport. Moreover, transport from day to night is horizontal circulation, not vertical convection; its relevant competition is atmospheric advection time versus chemical relaxation time, giving horizontal chemical quenching. Convection can affect either hemisphere indirectly through connected vertical transport; strong deep convection alone does not guarantee a quenched observable composition.
The two measurements sample different atmospheric regions and different radiative transfer geometries. An exoplanet emission spectrum probes the dayside; an exoplanet transmission spectrum probes the morning and evening limbs of the day-night terminator. Several alternatives to an exoplanet cloud deck can therefore suppress the transmission feature.
Temperature, mean molecular weight, limb chemistry, continuum opacity and the dayside temperature gradient are alternatives or degeneracies to test. In particular, the three-scale-height amplitude alone cannot establish different CO abundances between the hemispheres.
Four mechanisms that can produce disequilibrium chemistry in an exoplanet atmosphere are:
The exoplanet transport and photochemical examples follow kinetic atmosphere calculations and models including horizontal transport; the condensate example is examined in cold-trap calculations.
Take the logarithm to base ten and write pressure in units of , so its argument is dimensionless. Continuity of the atmospheric pressure-temperature profile gives
Thus
If the logarithm means , the equivalent constant is . A plot of temperature against logarithmic pressure is vertical in each isothermal region and straight between the two endpoints.
The processes can be organized by the supplied pressure ranges, although the exact boundaries require reaction rates, irradiation and mixing information:
The profile identifies plausible chemical regimes, but does not fix their transition pressures by itself. In particular, cloud formation depends on the species-specific condensation curve, and ultraviolet processing depends on shielding.